Processes for synthesis of 1,3,3,3-tetrafluoropropene

ABSTRACT

Disclosed is a process for the synthesis of 1,3,3,3-tetrafluoropropene that comprises, in one preferred embodiment, providing a compound of the formula CF 3 CH 2 CHFX, wherein X is a selected from the group consisting of chlorine, bromine and iodine, and exposing said compound to reaction conditions effective to convert said compound to 1,3,3,3-tetrafluoropropene. Other processes for forming 1,3,3,3-tetrafluoropropene are also disclosed.

FIELD OF THE INVENTION

The present invention relates to methods for the preparation oftetrafluorinated propene. More specifically, this invention concernsprocesses for the preparation of tetra fluoropropene in general and1,3,3,3-tetrafluoropropene, CF₃CH═CHF, (HFO-1234 ze).

BACKGROUND OF THE INVENTION

Tetrafluoropropenes are known to be useful as monomers in thepreparation of various homopolymers and copolymers. For example, U.S.Pat. No. 3,472,826 describes tetrafluoropropene as a co-monomer in theproduction of polyethylene. U.S. patent application Ser. No. 10/694,273,which is assigned to the assignee of the present invention, disclosesthe use of CF₃CH═CFH as a refrigerant with low global warming potentialand also as a blowing agent for use in connection with the formation ofvarious types of foams. In addition, CF₃CH═CFH can also befunctionalized to variety of compounds useful as intermediates formaking industrial chemicals.

Several methods of preparing tetrafluoropropene compounds are known. Forexample, U.S. Pat. No. 6,548,719 B1 describes generally the productionof a wide range of fluoroolefins by dehydrohalogenating, in the presenceof a phase transfer catalyst, a compound of formula CF₃C(R¹ _(a)R²_(b))C(R³ _(c)R⁴ _(d)) with at least one alkali metal hydroxide, wherethe R substituents are as defined in the patent, provided that at thereis at least one hydrogen and one halogen on adjacent carbon atoms. Thispatent, while disclosing a process that is efficient and useful for thepreparation of numerous tetrafluoropropenes, does not disclose a processspecifically for the preparation of 1,3,3,3-tetrafluoropropene.Moreover, in certain applications, it may be disadvantageous to followthe requirement of this patent which requires that at there is at leastone hydrogen and one halogen on adjacent carbon atoms.

The preparation of 1,3,3,3-tetrafluoropropene is disclosed in U.S. Pat.No. 5,986,151. This patent discloses a process comprising catalyticdehydrofluorination of CF₃CH₂CF₂H in the gas phase to afford CF₃CH═CHF.The preparation of 1,3,3,3-tetrafluoropropene is also disclosed in U.S.Pat. No. 6,124,510. This patent also discloses a process comprisingcatalytic dehydrofluorination of CF₃CH₂CF₂H in the gas phase. Each ofthese patents has the disadvantage of being limited to the use of1,1,1,3,3-pentafluoropropane (“245fa”) as a starting reactant, which maybe undesirable for reasons of cost, availability, and/or for otherreasons, such as the fact that multiple steps are frequently required tomanufacture HFC-245fa.

SUMMARY OF THE INVENTION

Applicants have discovered a process for the synthesis oftetrafluoropropene in general, and particularly1,3,3,3-tetrafluoropropene, that overcomes at least the deficiencies ofthe prior art noted above. The processes of the present invention in oneembodiment generally comprise providing a compound of the formula (I)CF₃CH₂CHFX, wherein X is selected from the group consisting of fluorine,chlorine, bromine and iodine (and in preferred embodiments consisting ofchlorine, bromine and iodine), and exposing said compound to reactionconditions effective to convert said compound of formula (I) to1,3,3,3-tetrafluoropropene. For the purposes of convenience but not byway of limitation, this process is sometimes referred to herein as “thedehydrohaolgentaion process.”

The processes of the present invention in another embodiment generallycomprise (a) reacting a compound of the formula (I) CHFX₂ with acompound of the formula (II) CH₂═CF₂, wherein each X is independentlyselected from the group consisting of fluorine, chlorine, bromine andiodine, to produce a reaction product comprising a compound of formula(III) CHXFCH₂CXF₂, wherein X is as described above, and:and (b) exposingsaid compound to reaction conditions effective to convert said compoundof formula (III) to 1,3,3,3-tetrafluoropropene. For the purposes ofconvenience but not by way of limitation, this process is sometimesreferred to herein as “the addition process” since that is the firststep is preferred forms of the process.

The present invention is thus directed to processes for the productionof CF₃CH═CFH which are amenable to scale up from readily available andrelatively inexpensive starting materials.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention is directed to methods for the production of boththe cis- and trans-isomers of 1,3,3,3 tetrafluoro-2-propene, CF₃CH═CHF(hereinafter referred to collectively as “HFC-1234 ze”). For thepurposes of convenience, the dehydrohalogenation process and theadditions process will be described separately below.

Dehydrohalogenation Process

In preferred embodiments, the step of providing a compound of formula(I) CF₃CH₂CHFX, comprises: (a) reacting a compound of formula (II) CY₄with a compound of formula (III) CY₂═CY₂, and preferably formula (III)is compound of formula CH₂═CY₂, wherein each Y is independently selectedfrom the group consisting of hydrogen, fluorine, chlorine, bromine andiodine, provided that at least one Y in formula (II) is a halogen and atleast one Y on a first carbon of formula III is hydrogen and that atleast one Y on the other carbon of formula III is a halogen to produce areaction product comprising a compound of formula (IV) CY₃CH₂CHY₂, and(b) optionally fluorinating the compound of formula (IV) underconditions effective to produce a reaction product comprising a compoundof formula (I) CF₃CH₂CHFX.

It is contemplated that numerous and varied reaction conditions can beutilized with good effect for the reaction step (a) in view of theteachings contained herein. For example, the reaction step may comprisea liquid-phase or a gas phase reaction, either catalyzed or uncatalyzed.For liquid phase reactions, it is generally preferred that the reactionis conducted in the presence of a catalyst, preferably a ligatedCu-catalyst. The preferred ligands are amine and acetyl acetone ligands,as described in WO 9821171 A1, which is incorporated herein byreference.

The reaction (a) can be carried out in the presence of a solvent or inthe absence of a solvent. Although it is contemplated that numerousreaction temperatures and pressures can be utilized for liquid phasereactions, it is generally preferred that the reaction is carried out ata temperature of from about 0° C. to about 300° C., more preferably fromabout 20° C. to about 250° C., and even more preferably from about 150°C. to about 250° C. The pressure of the reaction is preferably fromabout 5 psig to about 10 psig, and even more preferably form about 5psig to about 6 psig.

The optional fluorination step is preferably utilized when the reactionstep (a) produces a compound of the formula (IV) CY₃CH₂CHY₂ wherein lessthan four of said Y are fluorine. It is contemplated that numerousvariations of fluorination conditions are effective for the purposes ofthe present invention, and all such conditions are within the broadscope of the invention. It is contemplated that fluorination can takeplace in either the gas or the liquid phase, although gas phasefluorination is generally preferred. For gas phase fluorination, it isgenerally preferred to utilize a catalyzed, preferably a Cr-oxide(Cr₂O₃) catalyzed, gas-phase fluorination at a temperature of from about250° C. to about 500° C. in the presence HF, preferably anhydrous HFgas. In certain preferred embodiments, a flow reactor is used for thefluorination reaction. The fluorination reaction generally produces areaction product comprising CF₃CH₂CHFY and/or CF₃CH₂CHF₂, where Y is ahalogen other than F.

After the reaction step (a) or after the optional fluorination step wheneither of them is used, the present invention requires exposing thecompound of formula (I) CF₃CH₂CHFX to reaction conditions effective toproduce a reaction product comprising 1,3,3,3-tetrafluoropropene. Inpreferred embodiments, the exposing step comprises dehydrohalogenatingthe compound of formula (I). Although it is contemplated that numerousdehydrohalogenation steps can be utilized with good effect in accordancewith the teachings contained herein, it is preferred in certainembodiments that this step comprises contacting the compound of formula(I) with a catalyst at a relatively elevated temperature for a timesufficient to convert the compound to 1,3,3,3-tetrafluoropropene.Certain preferred embodiments comprise introducing a stream containingthe compound of formula (I) into a reactor containing catalyst,preferably a bed of iron-based catalyst, more preferably FeCl₃,maintained at temperature of from about 200° C. to about 400° C. andunder conditions to produce a contact time of from about 2 seconds toabout 30 seconds. Preferably the reaction pressure is maintained at apressure of from about 0 psig to about 200 psig. The exposing step mayalso be conducted in accordance with the teachings of U.S. Pat. No.6,548,719 B1, which is assigned to the assignee of the present inventionand which is incorporated herein by reference. Gas phasedehydrofluorination with an appropriate catalyst and at elevatedtemperature can also be performed in accordance with the procedures asdescribed in U.S. Pat. No. 5,986,151, which is also incorporated hereinby reference.

The exposing step preferably produces a reaction product stream whichcomprises 1,3,3,3-tetrafluoropropene, more preferably comprises a majorproportion of 1,3,3,3-tetrafluoropropene, and even more preferablycomprises from about 30% to at about 60% 1,3,3,3-tetrafluoropropene.

Any by-products contained in the reaction product stream can be removedto the extent desired by known means, such as distillation etc.

One particular embodiment of the present invention involves the reactionsteps set forth as Scheme 1, below:

Another particular embodiment involves the addition of CF₃X, wherein Xis a hydrogen or halogen as described above (preferably iodine orbromine), to FHC═CH₂, as illustrated in Scheme 2 below:

The addition reaction can be conducted in accordance with the generalprocedures described in Haszeldine et. al; J. Chem. Soc. 1970, (3),414-421. As can be seen from the above, the optional fluorination stepis not preferred for use in the illustrated embodiment. It should alsobe noted that both CF₃CFH—CH₂X, and CF₃CH₂CFHX, where X is halogen, maybe formed as a result of the addition reaction in embodiments of thetype disclosed in Scheme 2 and dehydrohalogenation affords HFO-1234yfand HFO-1234ze (cis- and trans-) respectively. The normal boiling pointof HFO-1234yf, which is about −28° C., and HFO-1234ze, which are about−19° C. and +9° C. for trans- and cis-respectively, are sufficientlydifferent to permit their separation by fractional distillation.

Applicants note that while CF₃H is relatively unreactive; the additionof CF₃H (X═H) to a fluoroolefin such as F₂C═CF₂ is known to occur (seeJ. Fluorine Chemistry, 2000, 102, 199-204 and WO 97022227 A1). Accordingto certain embodiments, therefore, addition of CF₃H and CFH═CHClproduces two compounds, namely, CF₃—CFH—CH₂C₁ and CF₃—CHCl—CFH₂, whichcan then be dehydrochlorinated to produce the desired compound, namely,CF₃CH═CFH.

Addition Process

The step of reacting a compound of formula (I) with a compound offormula (II) is amenable to a large number of specific processingcondition and steps in accordance with the teachings contained herein,and all such variations are within the broad scope of the presentinvention. For example, this reaction step may comprise a liquid-phaseor a gas phase reaction, either catalyzed or uncatalyzed. For liquidphase reactions, it is generally preferred that the reaction isconducted in the presence of a catalyst, preferably a ligatedCu-catalyst. In preferred embodiments, the step of reacting a compoundof formula (I) with a compound of formula (II) comprises a liquid-phaseC—C bond formation reaction, preferably conducted at a temperature offrom about 0° C. to about 200° C. and preferably in the presence ofligated Cu-catalyst. The preferred ligands are amine and acetyl acetoneligands as described in patent WO 9821171 A1, which is incorporatedherein by reference. Such preferred liquid phase reactions can beconducted in the presence or absence of a solvent.

It is contemplated that numerous and varied reaction conditions otherthan the preferred conditions specifically disclosed herein can beutilized with good effect for the reaction step (a) in view of theteachings contained herein. Although it is contemplated that numerousreaction temperatures and pressures can be utilized for liquid phasereactions, it is generally preferred that the reaction is carried out ata temperature of from about 0° C. to about 300° C., more preferably fromabout 20° C. to about 250° C., and even more preferably from about 150°C. to about 250° C. The pressure of the reaction is preferably fromabout 1 psig to about 20 psig, and even more preferably from about 1psig to about 10 psig.

Preferably, the step (b) of exposing a compound of the formula (III) toconditions effective to produce HFC-1234 ze comprises exposing saidformula (III) compound to relatively elevated temperatures in thepresence of two or more catalysts selected from the group consisting ofCr-based catalyst, Sn-based catalyst, and Fe-based catalyst. Morepreferably, the exposing step comprises introducing said formula (III)compound into a reactor containing a mixed catalyst reactor bed, whereinthe catalyst bed comprises Cr-, Sn- and Fe-salts. In such preferredembodiments, the reactor is preferably maintained at a temperature offrom about 300° C. to about 600° C., more preferably from about 350° C.to about 500° C., and even more preferably from about 450° C. to about500° C.

Without being bound by or to any particular theory of operation, it isbelieved that the preferred mixed catalyst reaction scheme disclosedherein produces reaction conditions in which both fluorination anddehydrofluorination reactions occur. Thus, it is contemplated, forexample, that CF₃CH₂CF₂H is produced as an intermediate and/or as abyproduct as a result of a portion of the preferred mixed catalyst bed,such as Fe-salts, which promote fluorination. Furthermore, it iscontemplated, without being necessarily bound to a theory of operation,that a portion of the mixed catalyst bed, such as FE-salt, promotesdehydrohalogenation of the compound (III) compound and/or fluorinatedintermediates produced in the reactor, thereby enhancing the productionof HFC-1234 ze.

The conditions of the preferred exposing step may be modified,particularly with regard to the dehydrofluorination reaction, inaccordance with the teachings of U.S. Pat. Nos. 5,986,151 and 6,548,719B1, each of which incorporated herein by reference.

The exposing step preferably produces a reaction product stream whichcomprises 1,3,3,3-tetrafluoropropene, more preferably comprises a majorproportion of 1,3,3,3-tetrafluoropropene, and even more preferablycomprises at least about 40% 1,3,3,3-tetrafluoropropene.

Any by-products contained in the reaction product stream can be removedto the extent desired by known means, such as distillation etc.

One particular embodiment of the present invention involves the reactionsteps set forth as Scheme 3, below:

The following examples are given as specific illustrations of theinvention. It should be noted that, however, that the invention is notlimited to the specific details set forth in the examples. All isomers(cis and trans) of CF₃CH═CFH are within the scope of the invention.

EXAMPLES Example 1 Synthesis of CF₃CH═CFH via reaction of CF₃I andCFH═CH₂

In an autoclave, a mixture of FHC═CH₂ (156 mmol) andtrifluoromethyliodide, CF₃I, (156 mmol) is heated at about 200° C. for48 hours. The resultant reaction product comprised a mixture ofcompounds, including CF₃CH₂CFHI. The CF₃CH₂CFHI is separated from themixture and purified by distillation to afford relatively pureCF₃CH₂CFHI. Crown ether (18-crown-6) (0.1 mmol) and CF₃CH₂CFHI (40 mmol)are added to 20 ml aq. solution of KOH (50 wt %) maintained at about 0°C. and heated to about 30-40° C. in an autoclav. The reactants in theautoclave was stirred for about 24 hours and gas chromatography of thevolatile material indicates that the reaction product comprises about 75mol % CF₃CH═CFH; the ratio of trans isomer to cis isomer is about 9to 1. NMR data: ¹⁹F (CDCl₃) δ=−61.3 (3F, m) and −120.0 (1F, ddq, J=77,15, and 9 Hz) ppm for trans; −58.4 (3, dd) and −110 (1F, ddq, J=78, 37and 16 Hz) ppm for cis.

Example 2 Synthesis of CF₃CH═CFH via reaction of CF₃Cl and CFH═CH₂

In an autoclave, a mixture of FHC═CH₂ (156 mmol) andtrifluoromethylchloride, CF₃Cl, (156 mmol) and catalyst Pd(Ph₃)₄ (0.1mol %) is heated at about 200° C. for 48 hours. The resultant reactionproduct comprised a mixture of compounds, including CF₃CH₂CFHCl. TheCF₃CH₂CFHCl is separated from the mixture and purified by distillationto afford relatively pure CF₃CH₂CFHCl. Crown ether (Aliquat® 336) (0.1mmol) and CF₃CH₂CFHCl (40 mmol) are added to 20 ml aq. solution of KOH(50 wt %) maintained at about 50° C. in an autoclave/pressure bottle.The mixture in the autoclave/pressure bottle is stirred for about 24hours and gas chromatography of the volatile material indicates that thereaction product comprises about mainly greater than about 65 mol %CF₃CH═CFH.

Example 3 Synthesis of CF₃CH═CFH via reaction of CF₃Br and CFH═CH₂

In an autoclave, a mixture of FHC═CH₂ (156 mmol) andtrifluoromethylbromide, CF₃Br, (156 mmol) and catalyst Pd(Ph₃)₄ (0.1 mol%) is heated at about 200° C. for 48 hours. The resultant reactionproduct comprised a mixture of compounds, including CF₃CH₂CFHBr. TheCF₃CH₂CFHBr is separated from the mixture and purified by distillationto afford relatively pure CF₃CH₂CFHBr. Tetrabutylammonium bromide (0.1mmol) and CF₃CH₂CFHBr (40 mmol) are added to 20 ml aq. solution of KOH(50 wt %) maintained at about 50° C. in an autoclave. The mixture in theautoclave is stirred for about 24 hours and gas chromatography of thevolatile material indicates that the reaction product comprises about 75mol % CF₃CH═CFH.

Example 4 Synthesis of CF₃CH═CFH form CCl₄

About 2 mol of CCl₄ and about 1 mol of CH₂═CHCl are stirred in anautoclave in the presence of about 0.005 mol of Cu-catalyst for about 6to about 20 hours and maintained at about 20° C. to about 100° C. Thereaction product mixture is separated and purified by distillation toprovide a stream comprising primarily CCl₃CH₂CHCl₂. The CCl₃CH₂CHCl₂thus produced is introduced at a flow rate of 0.05 to 0.5 lb/hr,together with about 0.1 to 1.5 lb/hr of HF, into a first catalyticreactor comprising 170 cc containing Cr₂O₃ or a mixture of Cr₂O₃ andother group-V1 metal oxides. The contact time in the reactor is fromabout 7 seconds to about 40 seconds and the reaction pressure is fromabout 5 to about 100 psig. The effluent from the reactor comprisesCF₃CH₂CHClF, at least a portion of which is subjected todehydrochlorination in as second catalytic reactor containing Ni-basedcatalysts maintained at a temperature of from about 400° C. to about700° C. The contact time in the second reactor is from about 2 to about30 seconds and the reaction pressure is from about 0 to about 200 psig.The effluent from the second reactor, which comprises CF₃CH═CFH, is thenprocessed by low temperature distillation to provide a relativelypurified product stream and providing CF₃CH═CFH in an overall yield offrom about 30% to about 40%.

Example 5 Synthesis of CF₃CH═CHF from CHCl₂F and H₂C═CF₂

CHCl₂F (2 mol) and CH₂═CF₂ (1 mol) are stirred in an autoclave in thepresence of 0.005 mol of Cu-catalyst for about 6 to about 20 hrs atreaction temperature of from about 20° C. to about 100° C. to produce areaction product comprising CHClFCH₂CClF₂. After separation andpurification as appropriate, by distillation for example, theCHClFCH₂CClF₂ thus obtained is passed at about 0.5 lb/hr flow rate overa mixed bed of catalyst comprising of Cr and Sn-salts at about 350° C.to about 700° C. to obtain CF₃CH═CHF in an amount constituting formabout 40% to about 65% over all isolated yields of CF₃CH═CFH.

Example 6 Synthesis of CF₃CH═CHF from CHI₂F and H₂C═CF₂

CHI₂F (2 mol) and CH₂═CF₂ (1 mol) are stirred in an autoclave in thepresence of 0.005 mol of Cu-catalyst for about 6 to about 20 hrs atreaction temperature of from about 20° C. to about 100° C. to produce areaction product comprising CHIFCH₂ClF₂. After separation andpurification as appropriate, by distillation for example, theCHIFCH₂ClF₂ thus obtained is treated with HF to afford CF₃CH₂CHIF at0-50° C. with SbCl₅ (5 mol %) catalyst which was passed at about 0.5lb/hr flow rate over a mixed bed of catalyst comprising of Cr andSn-salts at about 350° C. to about 700° C. to obtain CF₃CH═CHF in anamount constituting form about 40% to about 65% over all isolated yieldsof CF₃CH═CFH.

Example 7 Synthesis of CF₃CH═CHF from CHBr₂F and H₂C═CF₂

CHBr₂F (2 mol) and CH₂═CF₂ (1 mol) are stirred in an autoclave in thepresence of 0.005 mol of Cu-catalyst for about 6 to about 20 hrs atreaction temperature of from about 20° C. to about 100° C. to produce areaction product comprising CHIFCH₂ClF₂. After separation andpurification as appropriate, by distillation for example, theCHIFCH₂BrF₂ thus obtained fluorinated with HF as in example 6 to affordCF₃CH₂CFHBr and dehydrobrominated as above (example 6) to obtainCF₃CH═CHF. The isolated yields ranged from 40% to 65%.

Example 8 Synthesis of CF₃CH═CHF from CHIBrF and H₂C═CF₂

CHIBrF (2 mol) and CH₂═CF₂ (1 mol) are stirred in an autoclave in thepresence of 0.005 mol of Cu-catalyst for about 6 to about 20 hrs atreaction temperature of from about 20° C. to about 100° C. to produce areaction product comprising CHBrFCH₂ClF₂. After separation andpurification as appropriate, by distillation for example, theCHBrFCH₂ClF₂ thus obtained is passed at about 0.5 lb/hr flow rate over amixed bed of catalyst comprising of Cr and Sn-salts at about 350° C. toabout 700° C. to obtain CF₃CH═CHF in an amount constituting form about40% to about 65% over all isolated yields of CF₃CH═CFH.

1. A process for the synthesis of 1,3,3,3 tetrafluoropropene comprising:a) producing a compound having a structure according to formula (I)CF₃CH₂CXFH, wherein said producing involves reacting a compound offormula (II) CF₃X with a compound of formula (III) CH₂═CHY, wherein X isa halogen other than fluorine and Y is selected from the groupconsisting of fluorine, chlorine, bromine and iodine, and optionallyfluorinating an intermediate reaction product synthesized by saidreaction; and b) exposing said compound of formula (I) to reactionconditions effective to convert said compound to1,3,3,3-tetrafluoropropene.
 2. The process of claim 1 wherein saidreaction step a) is a liquid phase reaction.
 3. The process of claim 2wherein said reaction step a) comprises reacting said compound offormula (II) with said compound of formula (III) in the presence of aligated Cu-catalyst.
 4. The process of claim 3 wherein said ligatedCu-catalyst comprises an amine ligand.
 5. The process of claim 3 whereinsaid ligated Cu-catalyst comprises an acetyl acetone ligand.
 6. Theprocess of claim 1 wherein the exposing step c) comprisesdehydrohalogenating the compound of formula (I).
 7. The process of claim6 wherein dehydrohalogenating the compound of formula (I) comprisesintroducing a stream containing the compound of formula (I) into areactor containing FeCl₃ catalyst.
 8. The process of claim 7 whereinsaid reactor is maintained at temperature of from about 200° C. to about400° C.
 9. The process of claim 6 wherein said stream is introduced intosaid reactor under conditions to produce a contact time of from about 2seconds to about 30 seconds.
 10. The process of claim 1 wherein Y is F.11. The process of claim 1 wherein X is bromine or iodine.
 12. Theprocess of claim 1 wherein Y is Cl.
 13. A process for the synthesis of1,3,3,3 tetrafluoropropene a) reacting a compound of the formula (I)CHFX₂ with a compound of formula (II) CH₂═CF₂,to produce a reactionproduct comprising a compound of formula (III) CHXFCH₂CXF₂, wherein eachX is independently selected from the group consisting of chlorine,bromine and iodine, and wherein said reaction step (a) comprisesreacting said compound of formula (I) with said compound of formula (II)in the presence of a ligated Cu-catalyst; b) exposing said compound offormula (III) to reaction conditions effective to convert said compoundto 1,3,3,3-tetrafluoropropene.
 14. The process of claim 13 wherein saidexposing step comprises exposing said formula (III) compound in areactor to two or more catalysts selected from the group consisting ofCr-based catalyst and Sn-based catalyst.
 15. The process of claim 13wherein said exposing step comprises introducing said formula (III)compound into a reactor containing a mixed catalyst reactor bed, whereinthe catalyst bed comprises Cr-, Sn-salts.
 16. The process of claim 15wherein said reactor is maintained at a temperature of from about 300°C. to about 600° C.
 17. The process of claim 15 wherein said exposingstep comprises fluorinating said compound of formula (III) to produce afluorinated reaction product and dehydrofluorinating said fluorinatedreaction product to produce 1,3,3,3-tetrafluoropropene.
 18. The processof claim 13 wherein said reaction set (a) is a liquid phase reaction.19. The process of claim 18 wherein said ligated Cu-catalyst comprisesan amine ligand.
 20. The process of claim 19 wherein said ligatedCu-catalyst comprises an acetyl acetone ligand.